JPH1172966A - Image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming method by which a uniform toner coating layer without ghosts or blots can be obtd. on a developer carrying body and good image characteristics can be stably obtd. for a long time. SOLUTION: In this forming method, a negative charge toner 10 containing at least a binding resin and a charge controlling agent is carried by a developer carrying body 14 having a resin layer 13 formed on a metal base body 12, and then transferred from the developer carrying body to develop an electrostatic latent image on an electrostatic latent image holding body 7 to form a toner image. In this method, the charge controlling agent consists of a phenol deriv. compd. which is condensates of a phenol or its derivs. and aldehydes. The compd. contains at least two kinds of condensates with different numbers of units, and the condensates are chain condensates, cyclic condensates or a mixture of these.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to an image forming method including a step of developing an electrostatic image formed by electrophotography, electrostatic recording, and magnetic recording using toner.

[0002]

2. Description of the Related Art Conventionally, electrophotography has been disclosed in U.S. Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910.
Many methods are known, as described in Japanese Patent Application Publication No. JP-B-43-248 and JP-B-43-24748, and generally, an electric latent image (e.g., Electrostatic latent image), then develops the latent image with toner, and, if necessary, transfers the toner image to a transfer material such as paper. The toner is fixed to obtain a copy, and the toner remaining on the photoreceptor without being transferred is cleaned by various methods, and the above steps are repeated.

[0003] In recent years, such copying apparatuses have been strictly pursued to be smaller, lighter, faster, and have even higher reliability, reflecting changing market needs such as compounding and personalization. As a result, the performance required of the toner has been further enhanced.

On the other hand, the toner must have a positive or negative charge depending on the polarity of the electrostatic latent image to be developed. For this reason, it is generally known to add a dye, a pigment or a charge control agent. Have been. Today, negative triboelectric charge control agents known in the art include metal complexes of monoazo dyes, hydroxycarboxylic acids, dicarboxylic acids,
Metal complex salts such as aromatic diols, resins containing an acid component, and the like are known. Nigrosine dye,
Azine dyes, triphenylmethane dyes and pigments, quaternary ammonium salts, and polymers having quaternary ammonium salts in their side chains are known.

[0005] However, most of these charge control agents are colored and cannot be used for color toners. Most colorless, white, or light-colored toners applicable to color toners cannot be used in terms of performance.
They have drawbacks such as lack of uniformity of highlights and large fluctuations in image density in a durability test.

In addition, some charge control agents have the following disadvantages. It is difficult to balance image density and fog, it is difficult to obtain sufficient image density in a high humidity environment, poor dispersibility in resin, adversely affects storage stability and fixability.

Hitherto, several proposals have been made for condensates of phenol and aldehydes, including Japanese Patent Application Laid-Open No. Hei 2-201378. However, what is proposed in these publications is the addition of only a single unit of condensate.

Further, the cyclic condensate of a single unit conventionally added to a toner has a high melting point and low solubility in an organic solvent. Therefore, while a high charge amount can be obtained, it is not easy to disperse the toner in the toner. In particular, when a low-viscosity resin for a color toner is used, dispersion is likely to be insufficient, and toner scattering may be deteriorated. Also, with a single unit, it was not easy to adjust the chargeability. For example, when trying to obtain a high charge amount,
When the charging speed is reduced or the charging speed is conversely increased, the charging amount tends to be reduced.

However, in these conventional negative charge control agents,
Even if a sufficient amount of charge is not given to the toner, or even if a sufficient amount of charge is given to the toner, the toner is affected by other toner constituent materials, and excessive toner frictional charging or uneven charging may cause a blotch. This tends to cause an increase in toner cohesiveness, and a deterioration in development characteristics such as a decrease in image density and fog. Further, there is a problem of sleeve contamination that occurs when the charge control agent is missing from the toner and adheres to the surface of the sleeve as the developer carrier.

On the other hand, when the toner is brought into contact with a sleeve as a developer carrying member and frictionally charged, there is a problem how to stably and efficiently maintain proper charging for a long time.

As a sleeve in an image forming apparatus using an electrophotographic method, for example, a metal, an alloy thereof, or a compound thereof is molded into a cylindrical shape, and the surface thereof is made to have a predetermined surface roughness by electrolysis, blast, file, or the like. Is used. As general sleeve base materials, stainless steel, aluminum and nickel proposed in Japanese Patent Application Laid-Open No. 57-66455 are widely used.

However, when the toner is charged using these sleeves, it is difficult to adjust the charge amount of the toner. For example, when stainless steel is used as the sleeve base material, the charging power is strong. The toner existing near the surface of the sleeve has a very high electric charge, and is strongly attracted to the surface of the sleeve by the mirroring power, thereby forming an immobile layer. As a result, the chance of friction between the toner and the sleeve is reduced, and suitable charging is hindered. As a result, blotting, image density reduction and sleeve ghost are likely to occur due to non-uniform or excessive charging of the toner, and the developing characteristics are naturally deteriorated. "Sleeve ghost" means that when a large amount of toner on the sleeve is consumed due to solid development or the like, the toner in the immobile layer is also consumed, charging is performed properly again, and the density of the portion where the toner is consumed increases. This is the phenomenon.

When aluminum is used as the sleeve base material, the toner has a high charge-imparting ability, but has low durability due to the softness of the material, and tends to cause image deterioration due to surface wear. Therefore, there is a technology to coat or plate metal on the surface of the aluminum substrate in order to provide abrasion resistance.However, the durability is improved by improving the hardness of the sleeve surface, but compared to stainless steel etc.
Many of the toners had a small charge-imparting ability, and were liable to cause poor charging of the toner.

[0014]

SUMMARY OF THE INVENTION An object of the present invention is to provide an image forming method which solves the above-mentioned problems. That is, an object of the present invention is to obtain a uniform toner coat layer free of ghosts and blotches on a developer carrying member, and to obtain stable and high image density and low fog with high durability, that is, good long-term stability An object of the present invention is to provide an image forming method capable of obtaining various image characteristics.

[0015]

The above object is achieved by the following constitution.

A negatively chargeable toner containing at least a binder resin and a charge control agent is transported by a developer carrying member having a resin layer formed on a metal substrate, and the toner is formed on an electrostatic latent image holding member. An image forming method for developing an electrostatic latent image by transferring a negatively chargeable toner from a developer carrier to form a toner image, wherein the charge control agent is a phenol derivative, which is a condensate of phenol or a derivative thereof with an aldehyde A compound containing at least two types of condensates having different numbers of units, wherein the condensate is a chain condensate, a cyclic condensate, or a mixture thereof. You. Here, the “number of units” is defined as one unit of phenol unit, and the number of phenol units is defined as the number of units.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION By using a phenol derivative which is a condensate of phenol or a derivative thereof and an aldehyde, the present inventor has confirmed that good developing properties can be obtained without impairing the charging characteristics and powder characteristics of a negatively chargeable toner. Was found to be possible. Further, by using a developing sleeve for forming a resin layer on a metal substrate as a developing sleeve for frictionally charging the toner, excellent charging characteristics which have not been obtained in the past can be obtained. It was clarified that excellent development characteristics could be maintained.

The reason why the effect is achieved in the present invention will be described below.

The calixarene which has been conventionally proposed as a charge control agent is a cyclic substance, and the number of units has a single distribution. In contrast, the present invention contains two or more condensates having different numbers of units.

The first effect of this is that the charge decay characteristics become favorable. This is probably because the presence of condensates of various sizes allows small molecules to enter between large molecules, resulting in a change in electron conduction between the molecules. "Preferably the charge decay characteristic is preferable"
More specifically, it means that the charge is maintained when left unattended, or that leakage is performed so as not to have excessive charge during durability.

It has also been found that the toner after development behaves collectively by containing two or more kinds. 2
By containing more than one kind of condensate, transferability is improved, and transfer failure caused by unevenness of the paper during transfer is less likely to occur. Also, in the fixing step, the scattering of the fixing is reduced. This also seems to be related to the decay of charge after development.

The second effect of containing two or more kinds is that the yield at the time of synthesis is improved and the cost is reduced. This is because condensates having different numbers of units have different monomer conditions suitable for the reaction. Therefore, the remaining monomer in the course of the reaction may satisfy any one of the conditions, and it is considered that the amount of the monomer that does not contribute to the reaction decreases.

When two or more condensates having different numbers of units are contained, the crystallinity of the obtained powder is reduced. Therefore, fine particles can be formed with a weak force, and as a result, dispersibility in the toner resin is improved. These effects are further improved when the number of units is three or more, and it is preferable to include a condensate having 4 to 8 units, and more stable charging properties can be obtained. At this time, the abundance ratio of one condensate is preferably 90% or less, and more preferably 8%.
The effect is preferably 0% or less, particularly 70% or less, and when it is 60% or less, the above-mentioned effect becomes more remarkable.

Further, the substances which have been conventionally proposed as charge control agents are cyclic substances. On the other hand, since the present invention uses a plurality of condensates having different numbers of units, the condensate may have a chain structure or a component having a cyclic structure, and the respective effects are obtained. .

Since the chain condensate has excellent dispersibility, the chargeability is slightly inferior, but uniform chargeability is easily obtained. The cyclic compound is excellent in chargeability and thus poor in dispersibility, but can provide a high charge amount. These adverse effects are reduced by using a plurality of condensates having different numbers of units.
When a chain condensate and a cyclic condensate are used at the same time, their respective characteristics are utilized and the speed of the rise of charging also appears. The condensate having a chain structure softens from a relatively low temperature, like a general resin. By mixing this component and the cyclic component, good charging properties can be obtained as a result. This seems to be the following phenomenon. The cyclic component has high chargeability, but this component has cohesiveness, and dispersion may be poor. On the other hand, the chain component does not have a high charge amount, but is easily softened and has good dispersibility. Furthermore, since both have basically the same skeleton, they have an affinity and a fine mixed state is easily formed. In other words, the chain component is considered to be a dispersing aid for the cyclic component, so that uniform and high charging may be achieved.

As described above, when the condensate of the present invention is contained in the toner, a uniform charge level distribution of the toner at a high level can be obtained. For this reason, the high-temperature and high-humidity environment is an environment in which toner scattering is likely to occur.

Further, the toner used in the present invention is formed on the metal substrate in the process of triboelectric charging with the developer carrier, rather than using general stainless steel, aluminum, or metal plating as the material of the developer carrier. It was found that the use of a developing sleeve having a resin layer formed thereon provided much better charging ability.

This is due to the difference in chargeability between the toner and the material of each developer carrying member. That is, regarding the toner containing the phenol derivative condensate of the present invention, the chargeability with the developer carrier material is compared with the charge amount generated by contact with stainless steel, aluminum, metal plating, and the like. It was found that contact with a metal substrate having a layer (for example, a carbon black-dispersed resin layer) generates a larger amount of charge but does not result in excessive charging.

The condensate of the present invention can be obtained by heating phenols and aldehydes under alkaline conditions. A chain condensate and a cyclic condensate may be selectively obtained and then mixed. In order to selectively obtain the same, the conditions for adding the alkali metal may be adjusted, and the conditions for washing and extraction may be further adjusted. By adding a plurality of alkali metals, the types of condensates having different numbers of units can be increased. Various mixtures of a chain condensate and a cyclic condensate can be obtained by adjusting the heating temperature, the timing of adding the raw materials, the synthesis conditions such as the synthesis concentration, the amount of the solvent, the alkali metal, and the pH. Solvents that can be used for washing and extraction include acetone, methyl ethyl ketone, alcohol, ether, hexane, dioxane, toluene, chloroform, tetrahydrofuran, dimethyl sulfoxide and the like.

The terminal of the chain condensate of the present invention is a hydrogen atom,
Alkyl groups, alkyl groups including hydroxy groups are good,
Hydrogen and alkyl groups, which are advantageous in terms of charge in a high humidity environment, are preferred. For example, in the general formula (II), one is condensed to phenol, one is hydrogen or a hydroxy group, and in the general formula (I), one is condensed to an aldehyde, and one is hydrogen, an alkyl group or a hydroxyalkyl group. Becomes

The ratio of the chain condensate to the cyclic condensate in the condensate of the present invention is preferably from 1:20 to 30: 1. More preferably, the ratio is 1:10 to 20: 1. If the number of chains is less than 1:20, the formulation that exhibits the effect of improving dispersion is limited, and if it is not more than 1:10, the effect of a soft resin such as a color toner is reduced. In addition, when the chain-like material is contained at a ratio of 1:20 or more, charging suitable for development is quickly reached, and the toner supplied to the developing device is quickly replaced and consumed. 1: 1
By including 0 or more, replacement in a low-humidity environment is particularly fast. This makes it difficult to generate deteriorated toner at the time of durability, and improves image quality. Further, generation of toner having excessive charge (so-called charge-up) is reduced, and the transition of image density is stabilized.

Conversely, if the number of the ring-shaped toners is less than 30: 1, the toner formulation is limited when a high charge amount is required. When the number of the annular toner is less than 20: 1, it is difficult to apply the toner to a magnetic toner having a small particle diameter.

It is to be noted that, here, those having one unit are included in the chain condensate.

In the present invention, the condensate preferably contains units represented by the following general formulas (I) and (II).

[0035]

Embedded image [Wherein, i represents 0 or 1, and when i is 0, R ₁ has a hydrogen atom, a halogen atom, an alkyl group, an aryl group which may have a substituent, an aralkyl group, and a substituent. Alicyclic groups, fluoroalkyl groups,
Represents a nitro group, an optionally substituted sulfone group, an optionally substituted amino group or a trialkylsilyl group, and when i is 1, R ₁ is an alkyl group or an optionally substituted aryl Group, an aralkyl group, an optionally substituted alicyclic group, an optionally substituted amino group or a trialkylsilyl group, R ₂ represents a hydrogen atom, an alkyl group, a phenyl group, an aralkyl group, -C
OR ₅ (R ₅ represents a hydrogen atom or an alkyl group) or-
(CH ₂ ) _m COOR ₆ (R ₆ represents a hydrogen atom or an alkyl group, m represents an integer of 1 to 3), and R ₃ represents a hydrogen atom, an alkyl group, a halogen atom, a carboxyl group, a hydroxy group, Cyano group, nitro group, halogenated alkyl group, trialkylsilyl group, ester group having 1 to 8 carbon atoms, amino group which may be substituted, acyl group, sulfone group which may be substituted, And R ₄ represents a hydrogen atom, an alkyl group or an aryl group. ]

Further, a condensate containing a unit represented by the following general formula (III) is also used.

[0037]

Embedded image [R ₁ and R ₂ may be the same or different, and may have a hydrogen atom, a halogen atom, an alkyl group, an aryl group which may have a substituent, an aralkyl group, or a substituent. A good alicyclic group, a fluoroalkyl group, a nitro group, an optionally substituted sulfone group, an optionally substituted amino group or a trialkylsilyl group,
R ₃ and R ₄ may be the same or different and include a hydrogen atom, an alkyl group, a halogen atom, a carboxyl group, a hydroxy group, a cyano group, a nitro group, a halogenated alkyl group, a trialkylsilyl group, X ₁ , X ₂ , X ₃ , X ₄ represent an ester group of 1 to 8, an amino group which may be substituted, an acyl group, a sulfone group which may be substituted, and an ether group having 1 to 8 carbon atoms; Represents a linking position, may be linked to the unit represented by (I) or the unit represented by (III) via the unit represented by the general formula (II) to form a ring, and is a terminal In the case, it represents a hydrogen atom, an alkyl group or a hydroxyalkyl group. ]

The structure of the condensate of the present invention is applicable as long as the substituent Rn in the general formulas (I) to (III) does not inhibit the condensation reaction.

When the substituent R ₁ in the general formula (I) is an alkyl group, an aryl group which may have a substituent, an aralkyl group, or an alicyclic group, the charge amount is high and the charge rises. Tends to be good. Among them, a phenyl group, a cumyl group, a normal alkyl group, and a cycloalkyl group which may have a substituent are preferable, and more preferably at least one kind of phenyl group or 3 carbon atoms.
Those having the following alkyl groups or cycloalkyl groups having 8 or less carbon atoms are preferable since the charge retention is improved. In addition, by having a phenyl group, a methyl group, an ethyl group, a propyl group, a cyclopentyl group, and a cyclohexyl group, an appropriate charge amount can be maintained, and control in transfer and fixing becomes easy. This reduces the disturbance of the image during transfer and fixing.

Although there are substituents which have an adverse effect on the toner fixing performance, a methyl group, a phenyl group and a cyclohexyl group are preferred because they have no adverse effect.

Further, it is preferable to introduce a phenyl group or a methyl group into the starting phenol using p-phenylphenol or p-cresol in terms of ease of synthesis.

In the general formula (I), the substituent R ₂ is preferably a hydrogen atom, but other than that, an alkyl group and an aralkyl group are preferred.

The substituent R ₃ in the general formula (I) is preferably a hydrogen atom, but other than that, an alkyl group, a halogen atom and a nitro group are effective in improving the charge amount.

In the general formula (I), the substituent R ₄ is preferably a hydrogen atom, but the other group is preferably a methyl group because the methyl group does not inhibit the condensation reaction and does not contain impurities harmful to the toner performance.

Condensates having two or more units having different substituents are also preferred. By using two or more kinds, it is possible to adjust the crystallinity of the obtained powder, the dispersibility in the toner, and the way of rising of the charge. As a combination, for example, a combination of a phenyl group and a cyclohexyl group, a combination of a phenyl group and a methyl group, and a combination of a methyl group and a cyclohexyl group are preferable.

As a method for incorporating the compound of the present invention into a toner, there are a method of adding the compound into the toner and a method of externally adding the compound. When added internally, the amount is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the binder resin. Also,
When externally added, the amount is preferably 0.01 to 5 parts by mass.

The compounds of the present invention can also be used in combination with known charge control agents as described in the prior art.

Hereinafter, specific structures of the condensate of the present invention will be exemplified.

The abundance ratio is determined by measuring the molecular weight distribution using FD-MS (electrolysis desorption mass spectrometry), and determining the intensity ratio of the m / z peak as the abundance ratio. Calculate the molecular weight of each unit,
The molecular weight of the condensate composed of the unit is calculated to determine the unit configuration.

Condensate (1): A mixture of condensate composed of at least one unit selected from the following four units A and formaldehyde are starting materials (charge ratio: A: aldehyde = 1: 2) Between units Is linked with methylene

[0051]

Embedded image Example of structural formula

[0052]

Embedded image

[0053]

[Table 1]

Condensate (2): A mixture of a condensate composed of at least one unit selected from the same four units as condensate (1) A and formaldehyde are starting materials (charge ratio: A: aldehyde = 1: 2) Unit is linked by methylene

[0055]

Embedded image

[0056]

[Table 2]

Condensate (3): A mixture of condensate A composed of at least one unit selected from the same four units as condensate (1) A and formaldehyde as starting materials (charge ratio: A: aldehyde = 1: 2) Unit is linked by methylene

[0058]

[Table 3]

Condensate (4): A mixture of condensate composed of at least one unit selected from the following two units A and formaldehyde as starting materials (charge ratio: A: aldehyde = 1: 2) Between units Is linked with methylene

[0060]

Embedded image Example of structural formula

[0061]

Embedded image

[0062]

[Table 4]

Condensate (5): A mixture of condensate A composed of at least one unit selected from the same two units as condensate (4) A and formaldehyde are starting materials (charge ratio: A: aldehyde = 1: 2) Methylene bond between units An example of structural formula

[0064]

Embedded image

[0065]

[Table 5]

Condensate (6): A mixture of condensate A composed of at least one unit selected from the same two units as condensate (4) A and formaldehyde as starting materials (charge ratio: A: aldehyde = 1: 2) Unit is linked by methylene

[0067]

[Table 6]

Condensate (7): Mixture of condensate composed of at least one unit selected from the following three units A and formaldehyde as starting materials (charge ratio A: aldehyde = 1: 2) Between units Is linked with methylene

[0069]

Embedded image Example of structural formula

[0070]

Embedded image

[0071]

[Table 7]

Condensate (8): A mixture of condensate composed of at least one unit selected from the same three units as condensate (7) A and formaldehyde are starting materials (charge ratio: A: aldehyde = 1: 2) Methylene bond between units An example of structural formula

[0073]

Embedded image

[0074]

[Table 8]

Condensate (9): A mixture of condensate composed of at least one unit selected from the same three units as condensate (7) A and formaldehyde are starting materials (charge ratio: A: aldehyde = 1: 2) Unit is linked by methylene

[0076]

[Table 9]

Condensate (10): A mixture of condensates composed of at least one unit selected from the following six units: A, E and formaldehyde are starting materials (charge ratio: A:
E: aldehyde = 1: 1: 4) Bonded between units with methylene

[0078]

Embedded image

[0079]

[Table 10]

Condensate (11): A mixture of condensates composed of at least one unit selected from the following seven types of units A and E and formaldehyde are starting materials (charge ratio: A:
E: aldehyde = 1: 1: 4) Bonded between units with methylene

[0081]

Embedded image

[0082]

[Table 11]

Condensate (12): A mixture of condensates composed of at least one unit selected from the following five units: A, E and formaldehyde are starting materials (charge ratio: A:
E: aldehyde = 1: 1: 4) Bonded between units with methylene

[0084]

Embedded image

[0085]

[Table 12]

Condensate (13): A mixture of condensates composed of at least one unit selected from the following four units A, C and formaldehyde are starting materials (charge ratio: A:
C: aldehyde = 1: 1: 4) Bonded between units with methylene

[0087]

Embedded image

[0088]

[Table 13]

Condensate (14): A mixture of condensates composed of at least one unit selected from the following two units A and B and formaldehyde are starting materials (charge ratio: A:
B: aldehyde = 1: 1: 4) Bonded between units with methylene

[0090]

Embedded image

[0091]

[Table 14]

Condensate (15): A mixture of a condensate composed of at least one unit selected from units A, B and C. A, formaldehyde and acetaldehyde are starting materials (charge ratio: A: formaldehyde: acetaldehyde = 1) 1: 1.5)

[0093]

Embedded image

[0094]

[Table 15]

Condensate (16): A mixture of condensates composed of at least one unit selected from the following four units A (X is hydrogen) and formaldehyde are starting materials (charge ratio: A: aldehyde = 1 : 2)

[0096]

Embedded image

[0097]

[Table 16]

Condensate (17): A mixture of condensate composed of at least one unit selected from the following two units: A and formaldehyde as starting materials (charge ratio: A: aldehyde = 1: 2) Is bonded with methylene. Alkylation of the hydroxyl group is carried out by reacting butyl iodide after the condensation reaction.

[0099]

Embedded image

[0100]

[Table 17]

Condensate (18): A mixture A of a condensate composed of at least one unit selected from the following units A, B, C and D and at least one unit selected from units E and F: C, formaldehyde, and acetaldehyde are the starting materials (the charge ratio is A: C: formaldehyde: acetaldehyde = 1: 1: 2: 2).

[0102]

Embedded image

[0103]

[Table 18]

Condensate (19): A mixture of condensates composed of at least one unit selected from the following six units A, C, E and formaldehyde are starting materials (charge ratio is A: C: E: Aldehyde = 1: 1: 1: 6) Bonded between units with methylene

[0105]

Embedded image

[0106]

[Table 19]

Condensate (20): A mixture of condensates composed of at least one unit selected from the following six units A and C and formaldehyde are starting materials (charge ratio: A:
C: aldehyde = 1: 1: 4) Bonded between units with methylene

[0108]

Embedded image

[0109]

[Table 20]

As the binder resin used in the toner of the present invention, the following polymers can be used.

For example, homopolymers of styrene such as polystyrene, poly-p-chlorostyrene and polyvinyltoluene and their substituted products; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene Copolymer, styrene-acrylate copolymer, styrene-methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-
Styrene such as vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer -Based copolymer; polyvinyl chloride, phenolic resin, natural modified phenolic resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin , Xylene resin, polyvinyl butyral, terpene resin, coumarone indene resin, petroleum resin and the like can be used. Preferred binder resins include styrene copolymers and polyester resins.

Examples of comonomers for the styrene monomer of the styrene copolymer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, and acrylic acid.
Monocarboxylic acid having a double bond such as 2-ethylhexyl, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, and the like;
For example, dicarboxylic acids having a double bond such as maleic acid, butyl maleate, methyl maleate, dimethyl maleate and the like;
Vinyl esters such as vinyl acetate and vinyl benzoate; ethylene-based olefins such as ethylene, propylene, butylene; vinyl ketones such as vinyl methyl ketone and vinyl hexyl ketone; vinyl methyl ether and vinyl Vinyl monomers such as ethyl ether, vinyl isobutyl ether and the like; and vinyl monomers such as one or two or more are used.

The styrene-based polymer or styrene-based copolymer may be cross-linked or a mixed resin.

As a crosslinking agent for the binder resin, a compound having two or more polymerizable double bonds may be mainly used. For example, aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene and the like; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate and the like; Divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide and divinyl sulfone; and 3
Compounds having at least two vinyl groups are used alone or as a mixture.

The method for synthesizing the styrenic copolymer may be any of bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization.

In the bulk polymerization method, a polymer having a low molecular weight can be obtained by increasing the termination reaction rate by polymerizing at a high temperature, but there is a problem that the reaction is difficult to control.
In the solution polymerization method, a low molecular weight polymer can be easily obtained under mild conditions by utilizing the difference in radical chain transfer depending on the solvent and by adjusting the amount of the initiator and the reaction temperature.
It is preferable to obtain a low molecular weight polymer having a maximum molecular weight in a molecular weight range of 5,000 to 100,000 in the chromatogram of C.

As the solvent used in the solution polymerization, xylene, toluene, cumene, cellosolve acetate, isopropyl alcohol, benzene and the like are used. In the case of a styrene monomer mixture, xylene, toluene or cumene is preferred. It is appropriately selected depending on the polymer to be polymerized.

The reaction temperature varies depending on the solvent used, the initiator and the polymer to be polymerized.
It is better to carry out at 0 ° C. In solution polymerization, solvent 100
It is preferable to carry out with 30 parts by mass to 400 parts by mass of the monomer with respect to parts by mass.

Further, it is preferable to mix another polymer in the solution at the end of the polymerization, and several kinds of polymers can be mixed well.

Further, as a polymerization method for obtaining a high molecular weight polymer or a crosslinked polymer having a maximum value of the molecular weight in a region having a molecular weight of 100,000 or more in a GPC chromatogram,
Emulsion polymerization and suspension polymerization are preferred.

Among them, the emulsion polymerization method is a method in which a monomer (monomer) almost insoluble in water is dispersed as small particles in an aqueous phase with an emulsifier, and polymerization is carried out using a water-soluble polymerization initiator. . In this method, it is easy to control the heat of reaction, and since the phase in which the polymerization is carried out (the oil phase composed of the polymer and the monomer) and the aqueous phase are different, the termination reaction rate is small, and as a result, the polymerization rate is large. , With a high degree of polymerization.
Further, the reason is that the polymerization process is relatively simple, and that the polymerization product is fine particles, so that it is easy to mix with a colorant, a charge control agent, and other additives in the production of a toner. This is advantageous as compared with other methods as a method for producing a binder resin for a toner.

However, the resulting polymer tends to be impure due to the added emulsifier, and an operation such as salting out is required to take out the polymer. Therefore, suspension polymerization is a simple method.

In the suspension polymerization, 100 parts by mass or less of the monomer (preferably 1 part by mass) is added to 100 parts by mass of the aqueous solvent.
(0 to 90 parts by mass). Examples of usable dispersants include polyvinyl alcohol, partially saponified polyvinyl alcohol, calcium phosphate, and the like. There is an appropriate amount in terms of the amount of the monomer relative to the aqueous solvent, and generally 0.05 to 1 based on 100 parts by mass of the aqueous solvent. Used in parts by weight. The polymerization temperature is suitably from 50 to 95 ° C, but should be appropriately selected depending on the initiator used and the intended polymer. As the type of initiator, any initiator that is insoluble or hardly soluble in water can be used.

The initiators used in these polymerization methods include t-butyl peroxy-2-ethylhexanoate, cumin perpivalate, t-butyl peroxy laurate, benzoyl peroxide, lauroyl peroxide, octa-peroxy. Noyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile) 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1-bis (t-butylperoxy) 3 , 3,5-Trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,4-bis (T-butylperoxycarbonyl) cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl4,4-bis (t-
Butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane, 1,3-bis (t-butylperoxy-isopropyl) benzene, 2,5-dimethyl-2,5-di (t- Butylperoxy) hexane, 2,
5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, di-t-butyldiperoxyisophthalate, 2,2 -Bis (4,4-di-t-butylperoxycyclohexyl) propane, di-t-butylperoxy α-methylsuccinate, di-t-butylperoxydimethylglutarate, di-t-butylperoxyhexa Hydroterephthalate, di-t-butylperoxyazelate, 2,5-dimethyl-2,5-di (t-
Butyl peroxy) hexane, diethylene glycol
Bis (t-butylperoxycarbonate), di-t-
Butyl peroxytrimethyl adipate, tris (t-
(Butylperoxy) triazine, vinyltris (t-butylperoxy) silane, etc., which can be used alone or in combination.

The amount is used at a concentration of 0.05 parts by mass or more (preferably 0.1 to 15 parts by mass) with respect to 100 parts by mass of the monomer.

The composition of the polyester resin used in the present invention is as follows.

Examples of the dihydric alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol and 1,5-pentanediol. , 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-
Hexanediol, hydrogenated bisphenol A, and bisphenol represented by formula (A) and derivatives thereof;

[0128]

Embedded image

(Wherein R is an ethylene or propylene group, x and y are each an integer of 0 or more, and
The average value of x + y is 0-10. )

Diols represented by the formula (B):

[0131]

Embedded image

(Wherein R ′ is —CH ₂ CH ₂ — or

[0133]

Embedded image X 'and y' are integers of 0 or more, and x '
The average value of + y 'is 0 to 10. ).

Examples of the divalent acid component include phthalic acid,
Benzenedicarboxylic acids such as terephthalic acid, isophthalic acid and phthalic anhydride or their anhydrides and lower alkyl esters; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or their anhydrides and lower alkyl esters; n- Alkenyl succinic acids or alkyl succinic acids such as dodecenyl succinic acid, n-dodecyl succinic acid, or anhydrides and lower alkyl esters thereof; fumaric acid, maleic acid, citraconic acid, unsaturated dicarboxylic acids such as itaconic acid or anhydrides, lower acids And dicarboxylic acids such as alkyl esters; and derivatives thereof.

Further, it is preferable to use a trivalent or higher valent alcohol component and a trivalent or higher valent acid component which also function as a crosslinking component.

The polyhydric alcohol component having a valency of 3 or more includes
For example, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol,
1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,
3,5-trihydroxybenzene and the like.

The polyvalent carboxylic acid component having three or more valences in the present invention includes, for example, trimellitic acid, pyromellitic acid, 1,2,4-benzenetricarboxylic acid,
2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,2
5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-
Octanetetracarboxylic acid, empol trimer acid, and anhydrides and lower alkyl esters thereof;

[0138]

Embedded image

(Wherein X is an alkylene or alkenylene group having 1 to 30 carbon atoms having at least one side chain having 1 or more carbon atoms), and their anhydrides and lower alkyl esters And polyvalent carboxylic acids and derivatives thereof.

The alcohol component used in the present invention is 40 to 60 mol%, preferably 45 to 55 mol%.
%, 60 to 40 mol% as an acid component, preferably 5%
It is preferably from 5 to 45 mol%.

It is also preferable that the content of the trivalent or higher polyvalent component is 1 to 60 mol% of all the components.

The polyester resin can also be obtained by a generally known condensation polymerization.

In the toner according to the present invention, in addition to the above-mentioned binder resin component, the following compounds may be contained at a ratio smaller than the content of the binder resin component. For example, silicone resin, polyurethane, polyamide, epoxy resin, polyvinyl butyral, rosin, modified rosin, terpene resin,
Phenol resins, copolymers of two or more α-olefins, and the like are included.

The glass transition point (Tg) of the binder resin used in the toner of the present invention is preferably 45 to 80 ° C., more preferably 50 to 70 ° C.

In the present invention, the following waxes are preferably contained in order to impart releasability to the toner. It is a wax having a melting point of 70 to 165 ° C and a melt viscosity at 160 ° C of 1000 mPa · s or less, and specific examples thereof include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, montan wax, ethylene, propylene, and butene-1. ,
Linear α-olefins such as pentene-1, hexene-1, heptene-1, octene-1, nonene-1, and decene-1, and branched α-olefins having a terminally branched moiety, Examples include olefin homopolymers having different positions of unsaturated groups or copolymers thereof.

Further, a modified wax obtained by forming a block copolymer with a vinyl-based monomer or performing a graft modification may be used.

The amount of the wax is preferably from 0.5 to 10 parts by mass, more preferably from 1 to 8 parts by mass, per 100 parts by mass of the binder resin. Incidentally, two or more kinds of waxes may be added in combination.

These waxes are used in the production of toner.
It may be added and mixed in the polymer component in advance. In such a case, it is preferable that the wax and the high molecular weight polymer are preliminarily dissolved in a solvent and then mixed with a low molecular weight polymer solution at the time of preparing the polymer component. As a result, phase separation in a micro region is moderated, re-aggregation of high molecular weight components is suppressed, and a good dispersion state with a low molecular weight polymer can be obtained.

The solid concentration of the polymer solution is preferably 5 to 70 parts by mass or less in consideration of dispersion efficiency, prevention of resin deterioration during stirring, operability, and the like. Preferably, the low-molecular polymer solution has a solid concentration of 5 to 60 parts by mass or less.

The method of dissolving or dispersing the high molecular polymer and the wax is performed by stirring and mixing. The stirring is preferably performed in a batch system or a continuous system.

As a method of mixing the low molecular weight polymer solution, it is preferable to add 10 to 1000 parts by weight of the low molecular weight polymer solution to 100 parts by weight of the solid content of the preliminary solution, and to carry out stirring and mixing. In this case, a batch type or a continuous type may be used.

Examples of the organic solvent used for mixing the solution of the resin composition include benzene, toluene, xylene, Solvent Naphtha No. 1, Solvent Naphtha No. 2, Solvent Naphtha No. 3, cyclohexane, ethylbenzene, Solvesso 100, Solvesso 150, and mineral spirits. Hydrocarbon solvents such as methanol, ethanol, iso-
Propyl alcohol, n-butyl alcohol, sec-
Alcohol solvents such as butyl alcohol, iso-butyl alcohol, amyl alcohol and cyclohexanol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ester solvents such as ethyl acetate, n-butyl acetate and cellosolve acetate; Examples include ether solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, and methyl carbitol. Among these, aromatic solvents, ketone solvents or ester solvents are preferred. These may be used as a mixture.

The method of removing the organic solvent is preferably a method of heating the organic solvent solution of the polymer, removing 10 to 80 parts by mass of the organic solvent under normal pressure, and removing the remaining solvent under reduced pressure. At this time, the organic solvent solution is preferably maintained at a temperature within the range of 200 ° C. from the boiling point of the organic solvent used.

If the boiling point is lower than the boiling point of the organic solvent, not only is the efficiency at the time of distilling off the solvent poor, but also an unnecessary shear force is applied to the polymer in the organic solvent, and the redispersion of each constituent polymer is promoted. May cause phase separation in unfavorable conditions. On the other hand, when the temperature is higher than 200 ° C., the polymer is depolymerized, an oligomer is generated by molecular cleavage, and impurities are mixed into the resin composition, which is not preferable.

Examples of the magnetic substance used in the present invention include iron oxides of magnetite, maghemite, and ferrite; metals such as iron, cobalt, and nickel; and aluminum, cobalt, copper, lead, magnesium, tin, zinc, and metals such as these. Antimony, beryllium, bismuth, cadmium,
Alloys of metals such as calcium, manganese, selenium, titanium, tungsten, vanadium and mixtures thereof are used.

The shape of the magnetic material used in the present invention may be a hexahedron, an octahedron, a decahedron, a dodecahedron, a tetrahedron, or a polyhedron having more planes, a needle, a scale, a sphere, an irregular shape. And the like are used. Among them, a polyhedron is preferably used. In the case of a magnetic material having a polyhedral shape, it is possible to physically prevent the magnetic material from detaching from the toner particles from the shape.

In the present invention, the magnetic material used for the toner is
BET specific surface area by nitrogen gas adsorption method is 1 to 40 m ²
/ G, preferably ² to 30 m ² / g, more preferably 3
２０20 m ² / g is good. According to the BET method, nitrogen gas was adsorbed on the sample surface using a specific surface area measuring device: Autosorb 1 (manufactured by Yuasa Ionics) according to the BET method.
The specific surface area is calculated using the BET multipoint method.

The saturation magnetization of the magnetic material is 79
In a magnetic field of 5.8 kA / m, 5-200 Am ² /
kg, preferably in the range of 10 to 150 Am ² / kg.

Furthermore, the residual magnetization of the magnetic material is 79
In a magnetic field of 5.8 kA / m, 1 to 100 Am ² /
kg, preferably 1 to 70 Am ² / kg.

The average particle size of the magnetic material is set to 0.1.
It is preferably from 0.5 to 1.0 μm, more preferably from 0.1 to 1.0 μm.
It is 0.6 μm, particularly preferably 0.1 to 0.4 μm.

In the present invention, the amount of the magnetic substance contained in the toner is from 10 to 200 parts by mass, preferably from 20 to 170 parts by mass, more preferably from 30 to 150 parts by mass, per 100 parts by mass of the binder resin.

In the present invention, the shape of the magnetic material is that observed with a transmission electron microscope and a scanning electron microscope.

The magnetic properties of the magnetic material were measured using an “oscillating sample magnetometer VSM-3S-15” (manufactured by Toei Kogyo Co., Ltd.) under an external magnetic field of 795.8 kA / m.

In the toner of the present invention, charging stability,
In order to improve developability, fluidity, and durability, it is preferable to add silica, alumina, or titania fine powder.

[0165] The fine powder used in the present invention has a specific surface area by the BET method by nitrogen adsorption 2.0 m ² / g or more, particularly in the range of 50 to 400 m ² / g give good results. Silica fine powder is added to 100 parts by mass of toner.
It is good to use from 01 to 8 parts by mass, preferably from 0.1 to 5 parts by mass.

The fine powder used in the present invention may be used, if necessary, for the purpose of hydrophobicity, charge control, etc., with silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane coupling agents, It is also preferable to be treated with a treating agent such as a silane compound having a group or another organosilicon compound, or with a combination of various treating agents.

Other external additives may be added to the toner of the present invention, if necessary.

For example, there are resin fine particles and inorganic fine particles which function as a charge auxiliary agent, a conductivity-imparting agent, a fluidity-imparting agent, an anti-caking agent, a releasing agent at the time of fixing with a heat roller, a lubricant, an abrasive and the like.

Examples of the lubricant include Teflon powder, zinc stearate powder, polyvinylidene fluoride powder and the like, and among them, polyvinylidene fluoride powder is preferable. Examples of the polishing agent include cerium oxide powder, silicon carbide powder, and strontium titanate powder, and among them, strontium titanate powder is preferable. Examples of the fluidity-imparting agent include a titanium oxide powder and an aluminum oxide powder, and among them, a hydrophobic agent is preferable. Examples of the conductivity-imparting agent include carbon black powder, zinc oxide powder, antimony oxide powder, and tin oxide powder. Still further, a small amount of white fine particles and black fine particles of opposite polarity can be used as a developing property improver.

As the colorant that can be used in the toner of the present invention, any suitable pigment or dye can be used. As a colorant of the toner, for example, carbon black as a pigment,
Examples include aniline black, acetylene black, naphthol yellow, hansa yellow, rhodamine lake, alizarin lake, bengalara, phthalocyanine blue, and indanthrene blue. These are used in an amount necessary and sufficient to maintain the optical density of the fixed image, and 0.1 to 20 parts by mass, preferably 0.2 to 10 parts by mass, per 100 parts by mass of the resin.
Good addition amount of parts by mass. A dye is further used for the same purpose. For example, there are azo dyes, anthraquinone dyes, xanthene dyes, and methine dyes.
0.1 to 20 parts by mass, preferably 0.3 part by mass
The addition amount of 10 to 10 parts by mass is good.

To prepare the toner of the present invention, a binder resin, a phenol derivative condensate, and if necessary, a magnetic substance, a wax, a metal salt or metal complex, a pigment or a dye, and other additives are added to Henschel. After sufficiently mixing with a mixer such as a mixer or a ball mill, the mixture is melt-kneaded using a hot kneader such as a heating roll, kneader, or extruder, and then cooled and solidified, then pulverized and classified, and, if necessary, further added as desired. The agent is sufficiently mixed by a mixer such as a Henschel mixer to obtain the toner of the present invention.

In recent years, the toner particle diameter has been reduced, and even when the volume average particle diameter is 10 μm or less,
The uniformity of charging is promoted, the cohesiveness of the toner is also reduced, and the developability such as improvement of image density and fog is improved. In particular, the effect is remarkable in a toner having a volume average particle diameter of 6.0 μm or less, and an extremely high-definition image can be obtained. It is preferable that the volume average particle size is 2.5 μm or more, since sufficient image density can be obtained. On the other hand, if the particle size of the toner is reduced, the condensate is likely to be liberated. However, the toner of the present invention maintains excellent developability since the condensate of the present invention has excellent dispersibility.

The volume average particle diameter of the magnetic toner of the present invention was determined using a Coulter Multisizer (manufactured by Coulter Inc.), and the electrolytic solution was ISOTON R-II (1% aqueous NaCl solution,
(Coulter Scientific Japan). As a measuring method, the electrolytic aqueous solution 100 to
0.1 to 5 m of a surfactant as a dispersant in 150 ml
and 2 to 20 mg of the measurement sample. The electrolyte in which the sample is suspended is subjected to a dispersion treatment for about 1 to 3 minutes by an ultrasonic disperser, and the volume and the number are measured by the measuring device to calculate a volume average particle diameter.

100 when the volume average particle size is 6 μm or more.
When measuring a particle of 2 to 60 μm using an aperture of μm, and measuring a particle of 1 to 30 μm using an aperture of 50 μm when the volume average diameter is 6 to 2.5 μm, and when the volume average particle diameter is less than 2.5 μm, Particles of 0.6-18 μm are measured using a 30 μm aperture.

Next, the structure of the sleeve which is the developer carrying member of the present invention will be described with reference to FIG.

The sleeve as the developer carrying member of the present invention is
Cylindrical substrate and coating layer (resin layer) covering the surface of the substrate
Having. The resin layer 1 contains a binder resin 4, and in some cases, a conductive substance 2, a filler 3, a solid lubricant 5, and the like, and is coated on a cylindrical substrate 6. When a conductive material is contained, excessive charge of the toner can be prevented since the resin layer 1 is conductive. When the filler 3 is contained, abrasion of the resin layer 1 by the toner is prevented, and further, charging of the toner can be suitably controlled by the charge imparting property of the filler 3. When the solid lubricant 5 is contained, the releasability of the toner from the sleeve is improved, and as a result, the fusion of the toner onto the sleeve can be prevented.

When the conductive material is contained in the resin layer of the developer carrying member in the present invention, the volume resistance of the resin layer is 10%.
^The resistance is preferably ⁶ Ω · cm or less, more preferably 10 ³ Ω · cm or less. If the volume resistance of the resin layer exceeds 10 ⁶ Ω · cm, toner charge-up is likely to occur,
It may cause blotching and deterioration of development characteristics.

The volume resistance of the resin layer was determined by coating and drying the insulating composition on a insulating sheet with a bar coater.
It can be cut into 10 cm × 10 cm, and can be measured with a low resistivity meter Loresta (Mitsubishi Yuka Co., Ltd.).

The surface roughness of the resin layer is preferably in the range of 0.2 to 3.5 μm in JIS center line average roughness (Ra). If Ra is less than 0.2 μm, the charge amount of the toner in the vicinity of the sleeve becomes too high, the toner is attracted to the sleeve by the mirroring power, new toner cannot be charged by the sleeve, and the developing property is insufficient. Become. When Ra exceeds 3.5 μm, the toner coating amount on the sleeve is excessively increased, so that a sufficient charge amount of the toner cannot be obtained, and the toner becomes non-uniformly charged, which causes a reduction in image density and density unevenness.

Next, each material constituting the conductive resin layer 1 will be described.

In FIG. 1, the conductive substance 2 includes, for example, metal powders such as aluminum, copper, nickel and silver; metal oxides such as antimony oxide, indium oxide and tin oxide; carbon fibers, carbon black, graphite and the like. And carbon allotropes. Among them, carbon black is particularly excellent in electric conductivity, and is preferably used because it can be filled with a polymer material to impart conductivity, or by controlling the amount of addition, a certain degree of conductivity can be obtained. The carbon black used in the present invention has a number average particle diameter of 1 μm or less, preferably 0.01 μm to 0.1 μm.
It is preferably 8 μm. If the number average particle size of the carbon black exceeds 1 μm, it becomes difficult to control the volume resistance of the resin layer, which is not preferable.

[0182] The amount of the conductive substance used is as follows.
The amount is preferably from 0.1 to 300 parts by mass, more preferably from 1 to 100 parts by mass, per 100 parts by mass.

Examples of the filler 3 include inorganic compounds such as alumina, asbestos, glass fiber, calcium carbonate, magnesium carbonate, barium carbonate, barium sulfate, silica and calcium silicate; phenol resins, epoxy resins, melamine resins, silicone resins , PMMA, methacrylate terpolymers (eg, polystyrene / n-butyl methacrylate / silane terpolymer), styrene-butadiene copolymers, polycaprolactam, polyvinylpyridine, nitrogen-containing compounds such as polyamides; polyvinylidene fluoride, polyvinyl chloride , Polytetrafluoroethylene, polytetrachlorofluoroethylene, perfluoroalkoxylated ethylene, polytetrafluoroalkoxyethylene, fluorinated ethylene propylene-polytetrafluoroe Ren copolymer, trifluorochloroethylene - highly halogenated polymers such as vinyl chloride copolymers; Other polycarbonates, polyesters, and the like. Among them, silica and alumina are preferably used because they have their own hardness and charge controllability to the toner.

The amount of the filler used is 100
It is preferably 0.1 to 500 parts by mass, more preferably 1 to 200 parts by mass with respect to parts by mass.

Examples of the solid lubricant 5 include molybdenum disulfide, silicon nitride, graphite, graphite fluoride, silver-niobium selenide, calcium chloride-graphite, and talc. Of these, graphite is preferably used because it has conductivity as well as lubricity, has a function of reducing toner having an excessively high charge, and has a charge amount effective for development.

The amount of the solid lubricant used is as follows.
The amount is preferably from 0.1 to 300 parts by mass, more preferably from 1 to 150 parts by mass, per 100 parts by mass.

Examples of the conductive material 2, and in some cases, the binder 3 in which the filler 3 and the solid lubricant 5 are dispersed are phenolic resins, epoxy resins, polyamide resins,
Known resins such as polyester resin, polycarbonate resin, polyolefin resin, silicone resin, fluorine resin, styrene resin, and acrylic resin are used. Particularly, a thermosetting or photocurable resin is preferable.

In the present invention, the conductive material in the resin layer on the sleeve surface, or in some cases, a filler or a solid lubricant is preferably exposed to the surface, or the surface is smoothed to obtain a uniform unevenness. In order to form the surface, it is possible to impart more preferable performance by performing a smoothing treatment on the surface by means such as polishing described below.
In particular, it is effective for the vertical streak phenomenon that occurs in solid black and halftone images and the rise of the initial image density, and is particularly effective under high temperature and high humidity.

The operation of the present invention will be described with reference to FIG. In FIG. 2A, the coating layer (resin layer) 501 includes a solid lubricant 50.
2, conductive substance 503, filler 504, binder resin 505
And coated on the cylindrical substrate 506. This is polished with a belt-like abrasive material to which felt or abrasive grains are adhered, so that the surface unevenness of the sleeve can be uniformly finished as shown in FIG. 2 (B). As a result, only the toner that has been frictionally charged with the sleeve is conveyed to the developing area. Therefore, it is considered that the above effects can be obtained.

Even after the smoothing treatment as described above, the surface of the coat layer has a Ra of JIS B 0601 of 0.
It is preferable to maintain irregularities in a range of 2 to 3.5 μm, and more preferably to have irregularities of about 0.3 to 2.5 μm. The reason is the same as above.

Next, a description will be given of a developing method in which the developing sleeve as the developer carrying member of the present invention is incorporated.

In FIG. 3, an image carrier for carrying an electrostatic latent image formed by a known process, for example, an electrophotographic photosensitive drum 7 is rotated in the direction of arrow B. The developing sleeve 14 as a developer carrying member carries the toner 10 as a one-component developer supplied from the hopper 9 and
By rotating in the manner, the toner 10 is transported to the developing section D where the developing sleeve 14 and the photosensitive drum 7 are opposed.
When the toner 10 is a magnetic toner, a magnet 11 is disposed in the developing sleeve 14 for magnetically attracting and holding the toner 10 on the developing sleeve 14. The toner 10 obtains a triboelectric charge capable of developing the electrostatic latent image on the photosensitive drum 7 by friction with the developing sleeve 14.

In order to regulate the layer thickness of the toner 10 conveyed to the developing section D, when the toner is a magnetic toner, a regulating blade 8 made of a ferromagnetic metal has a gap of about 200 to 300 μm from the surface of the developing sleeve 14. It is suspended from the hopper 9 so as to face the developing sleeve 14 with a certain width. When the magnetic lines of force from the magnetic pole N1 of the magnet 11 are concentrated on the blade 8, a thin layer of the toner 10 is formed on the developing sleeve 14. As the blade 8, a non-magnetic blade can be used. When the toner 10 is a non-magnetic toner, an elastic blade such as urethane rubber, silicone rubber, or a chip blade is used.

Toner 1 formed on developing sleeve 14
0 is the thickness of the developing sleeve 14 in the developing section D.
It is preferable that the distance be smaller than the minimum gap between the photosensitive drum 7 and the photosensitive drum 7. The present invention is particularly effective for a developing device of a type that develops an electrostatic latent image with such a thin toner layer, that is, a non-contact type developing device. However, the present invention is also applicable to a developing device in which the thickness of the toner layer in the developing section is equal to or greater than the minimum gap between the developing sleeve 14 and the photosensitive drum 7, that is, a contact type developing device.

In order to avoid the complication of the description, a non-contact type developing device will be described as an example in the following description.

A developing bias voltage is applied to the developing sleeve 14 from a power source 15 in order to fly the toner 10 as a one-component developer carried on the developing sleeve 14. When using a DC voltage as the developing bias voltage,
It is preferable that a voltage having a value between the potential of the image portion of the electrostatic latent image (the region where the toner 10 adheres and is visualized) and the potential of the background portion is applied to the developing sleeve 14. On the other hand, in order to increase the density of the developed image or improve the gradation, an alternating bias voltage is applied to the developing sleeve 14 so that the developing unit D
Alternatively, an oscillating electric field whose direction is alternately reversed may be formed. In this case, it is preferable to apply, to the developing sleeve 14, an alternating bias voltage on which a DC voltage component having a value between the potential of the image portion and the potential of the background portion is superimposed.

In so-called regular development in which toner is adhered to a high potential portion of an electrostatic latent image having a high potential portion and a low potential portion to visualize the toner, a toner charged to a polarity opposite to the polarity of the electrostatic latent image is used. On the other hand, in so-called reversal development, in which toner is adhered to a low potential portion of an electrostatic latent image to visualize the toner, a toner charged to the same polarity as the polarity of the electrostatic latent image is used.
Note that the high potential and the low potential are expressed by absolute values. In any case, the toner 10 is charged to a polarity for developing the electrostatic latent image by friction with the developing sleeve 14.

FIG. 4 is a block diagram showing another embodiment of the present invention.

In the developing device shown in FIG. 4, as a member for regulating the layer thickness of the toner 10 on the developing sleeve 14, a material having rubber elasticity such as urethane rubber or silicone rubber or a metal elastic material such as phosphor bronze or stainless steel is used. The elastic plate 17 is made of a material having the following characteristics.
4 is characterized by being pressed against. In such a developing device, a thinner toner layer can be formed on the developing sleeve 8. The other configuration of the developing device in FIG. 4 is basically the same as that of the developing device shown in FIG. 3, and the same reference numerals in FIG. 4 as those in FIG. 3 indicate the same members.

In the developing device shown in FIG. 4 in which the toner layer is formed on the developing sleeve 14 as described above, the toner is rubbed on the developing sleeve 14 by the elastic plate 17, so that the amount of triboelectric charge of the toner is large. Thus, the image density is improved.

Next, an example of an image forming method having a contact charging / transfer method of the present invention will be described with reference to the schematic configuration diagram of FIG.

Reference numeral 801 denotes a rotating drum type photosensitive member which is rotated clockwise in the drawing at a predetermined peripheral speed (process speed). Reference numeral 802 denotes a charging roller which is pressed against the surface of the photoconductor 801 with a pressing force, and is driven to rotate as the photoconductor 801 rotates. 803 denotes a charging bias current V ₂ for applying a voltage to the charging roller 802, the surface of the photosensitive member 801 is charged to a predetermined polarity and potential by a bias is applied to the charging roller 802. Next, image exposure 8
04 forms an electrostatic image, and the developing unit 805 sequentially visualizes the image as a toner image.

A bias V ₁ is applied to the developing sleeve constituting the developing means 805 from the bias applying means 813. The toner image formed on the latent image bearing member by development, contact transfer means transfer bias V ₃ applied 806
, And the toner image on the transfer material is heated and pressed by the heating and pressing means 811.
On the surface of the photoconductor 801 after the transfer of the toner image, adhered contaminants such as untransferred toner are cleaned by a cleaning device 809 having an elastic cleaning blade pressed against the photoconductor 801 in a counter direction.
The charge is eliminated by 0, and an image is repeatedly formed.

[0204]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited thereto.

(Production Example of Developer Carrier Having Resin Layer Formed on Surface) <Development Sleeve Production Example 1> Phenol resin intermediate 150 parts by mass Carbon black 5 parts by mass Crystalline graphite 45 parts by mass Methanol 41 parts by mass isopropyl alcohol 284 parts by mass

The phenol resin intermediate methanol solution was diluted with isopropyl alcohol (IPA), carbon black and crystalline graphite were added, and the mixture was dispersed by a sand mill using glass beads. Next, a resin layer was applied on the sleeve using this paint.

As the developing sleeve, the surface of a stainless steel cylindrical tube having an outer diameter of 32 mm and a wall thickness of 0.8 mm was polished to reduce the run-out of the cylindrical tube to 10 μm or less and the surface roughness to 4 μm or less in Rz notation. Was. The sleeve was set up vertically, rotated at a constant speed, masked at the upper and lower ends, and the coating material was applied while lowering the spray gun at a constant speed. Masking width at both ends of sleeve is 3m
m. After drying and curing at 160 ° C. for 20 minutes in a drying oven, a belt-shaped felt is rubbed against the surface of the resin-coated sleeve with a load of 4 kgf, and the surface is polished. Got a sleeve.

This resin layer has a thickness of 10 μm and a surface roughness R
a was 0.92 μm on average at 6 points, and the pencil hardness was measured and found to be 2H. A magnet was inserted into this sleeve, and flanges were attached to both ends to obtain a developing sleeve 1.

<Developing Sleeve Production Example 2> Phenol resin intermediate 150 parts by mass Carbon black 5 parts by mass Crystalline graphite 45 parts by mass PMMA fine powder (average particle diameter 0.5 μm) 25 parts by mass Methanol 58 parts by mass isopropyl alcohol 408 parts by mass Department

The above materials were dispersed using a sand mill. A methanol solution of the phenolic resin intermediate is diluted with a portion of isopropyl alcohol (IPA). Carbon black and crystalline graphite were added and dispersed by a sand mill using glass beads. Here, the above polymethyl methacrylate resin fine powder dispersed in the remaining IPA was further added as a filler, and the sand mill was further dispersed.

Next, using this coating material, a resin layer was coated on the developing sleeve in the same manner as in Production Example 1 for a resin-coated developing sleeve, and then the surface was polished. The thickness of this resin layer is 15 μm, and the surface roughness Ra is 1.15 μ on an average of 6 points.
m, and the pencil hardness was measured and found to be 3H. A magnet was inserted into this sleeve, and flanges were attached to both ends to form a developing sleeve 2.

<Developing Sleeve Production Example 3> Phenol resin intermediate 125 parts by mass Carbon black 5 parts by mass Crystalline graphite 45 parts by mass Methanol 41 parts by mass isopropyl alcohol 284 parts by mass

The methanol solution of the phenol resin intermediate was diluted with isopropyl alcohol (IPA), carbon black and crystalline graphite were added, and the mixture was dispersed by a sand mill using glass beads. Next, a resin layer was applied on the sleeve using this paint.

A developing sleeve was used by polishing the surface of an aluminum cylindrical tube having an outer diameter of 16 mm and a wall thickness of 0.8 mm so that the cylindrical tube had a run-out of 10 μm or less and a surface roughness of 4 μm or less in Rz notation. . The sleeve was set up vertically, rotated at a constant speed, masked at the upper and lower ends, and the coating material was applied while lowering the spray gun at a constant speed. Masking width at both ends of sleeve is 3m
m. After drying and curing at 160 ° C. for 20 minutes in a drying oven, a belt-shaped felt is rubbed against the surface of the resin-coated sleeve with a load of 4 kgf, and the surface is polished. Got a sleeve.

This resin layer has a thickness of 10 μm and a surface roughness R
a was 0.87 μm on average at 6 points, and the pencil hardness was further measured to be 2H. A magnet was inserted into this sleeve, and flanges were attached to both ends to form a developing sleeve 3.

<Developing Sleeve Comparative Manufacturing Example 1> As a developing sleeve, the surface of a stainless steel cylindrical tube having an outer diameter of 32 mm and a wall thickness of 0.8 mm was polished to reduce the deflection of the cylindrical tube to 10 μm.
m and a surface roughness of 4 μm or less in Rz notation, masking the upper and lower ends, and using a blasting machine with amorphous alumina abrasive grains (# 300) to give 3.92 ×
The blast treatment was performed at a blast pressure of 10 ^-2 MPa (4.0 kgf / cm). The masking width at both ends of the sleeve is 3
mm. The surface roughness Ra of the blasting sleeve was 1.09 μm on average at six points. A magnet was inserted into this sleeve, and flanges were attached to both ends to form a developing sleeve 4.

(Binder Resin for Toner) The binder resin used in the present invention is as follows. First, a styrene-butyl acrylate-monobutyl maleate copolymer A (St / BA / MBM = 78/2) using tris (t-butylperoxy) triazine as an initiator in a suspension polymerization method.
0/2, Tg = 67 ° C., Mw = 920,000). Then, a styrene-butyl acrylate-monobutyl malate copolymer B (St / BA / M
BM = 83/15/2, Tg = 61 ° C., Mw = 15.0
00). A mixture of 70 parts by mass of copolymer B and 30 parts by mass of copolymer A in a solution was used as a binder resin.

[0218] <Example 1> Binder resin 100 parts Magnetite 100 parts by mass (octahedron, the average particle diameter of ^{0.21μm, BET8.1m 2 /g,σs=85.1A m 2 /} kg, σr = 10.5 Am ² / kg) 4 parts by weight of low molecular weight polypropylene wax (melting point 130 ° C.) 2 parts by weight of condensate (1)

After the above materials were well mixed by a Henschel mixer, they were melt-kneaded by a twin-screw kneading extruder set at 130 ° C. The obtained kneaded material was cooled, coarsely pulverized by a cutter mill, and then finely pulverized using a fine pulverizer using a jet stream, and the obtained finely pulverized material was further classified by an air classifier to obtain a weight average particle size. A classified fine powder having a diameter of 5.5 μm was obtained.

To 100 parts by mass of the obtained classified fine powder, silica fine powder (BET specific surface area: 200 m
² / g) 20 hexamethyldisilazane per 100 parts by mass
1.2 parts by mass of the hydrophobic silica treated with parts by mass was added, mixed with a Henschel mixer, and sieved with a mesh having an opening of 150 μm to obtain a negatively chargeable one-component magnetic toner 1.

The following evaluation tests were performed on the obtained toner 1.

[Image Evaluation Test] Commercially available copying machine NP675
0 (manufactured by Canon Inc.), the developing sleeve was replaced with the developing sleeve 1 shown in the developing sleeve manufacturing example of the present invention, and 10000 copies were made under normal temperature / normal humidity environment, at normal temperature / low humidity environment, and In each environment of high temperature / humidity, 10,000 copies were made, and image density and fog were evaluated (evaluation environment: normal temperature / normal humidity (23 ° C./60% R)
H), room temperature / low humidity (23 ° C./5% RH), high temperature and high humidity (3
2.5 ° C / 80% RH)).

Also, after copying 10,000 sheets in a normal temperature / normal humidity environment, a part of the developing sleeve surface was wiped cleanly with ethanol, a solid black image was printed, and the image density before and after wiping with ethanol was measured. The sleeve contamination was evaluated by calculating the difference. Those having a small density difference Δ are good because they have little influence of contamination.

The image density was measured using a “Macbeth reflection densitometer” (manufactured by Macbeth). The fog is measured using a "reflection densitometer" (manufactured by Tokyo Denshoku Technology Center) to measure the reflection density of the transfer paper and the reflection density of the transfer paper after copying solid white, and the difference is used as the fog value. The smaller the value, the better the fog suppression.

[Sleeve Coat Evaluation Test] The toner coat on the sleeve was visually observed and the blotting generation level was classified into the following ranks (evaluation environment: normal temperature / normal humidity (23 ° C.)
/ 60% RH), room temperature / low humidity (23 ° C / 5% RH), high temperature and high humidity (32.5 ° C / 80% RH).

Blotch rank ◎ (excellent) No occurrence. ○ (Good) Slightly generated at the end of the sleeve. Δ (OK): Very slight occurrence, but no effect on image. × (impossible) It is clearly generated and affects the image.

The sleeve ghost has a density of 1.3 and a density of 0.3.
A solid image having a density of 1.0 was copied as an original after an alternating image of a line having a width of 20 mm and a length of 100 mm (process direction) of the original No. 05 as an original, and evaluation was made based on the difference in density of the 1.0 density portion. The smaller the density difference, the better the ghost level.

The evaluation results of the sleeve coat property test and the image evaluation test are summarized in Tables 1 to 3.

<Example 2> Classified fine powder and toner 2 were obtained in the same manner as in Example 1 except that condensate (1) was changed to condensate (2).

Each evaluation was performed on this toner 2 in the same manner as in Example 1. The evaluation results are summarized in Tables 1 to 3.

<Example 3> A classified fine powder and toner 3 were obtained in the same manner as in Example 1 except that condensate (1) was changed to condensate (3).

Each evaluation was performed on this toner 3 in the same manner as in Example 1. The evaluation results are summarized in Tables 1 to 3.

<Example 4> A classified fine powder and toner 4 were obtained in the same manner as in Example 1 except that condensate (1) was changed to condensate (6).

Each evaluation of this toner 4 was performed in the same manner as in Example 1. The evaluation results are summarized in Tables 1 to 3.

<Example 5> A classified fine powder and toner 5 were obtained in the same manner as in Example 1 except that the condensate (1) was changed to the condensate (9).

Each evaluation was performed on this toner 5 in the same manner as in Example 1. The evaluation results are summarized in Tables 1 to 3.

<Example 6> A classified fine powder and toner 6 were obtained in the same manner as in Example 1 except that the condensate (1) was changed to the condensate (10).

Each evaluation was performed on this toner 6 in the same manner as in Example 1. The evaluation results are summarized in Tables 1 to 3.

<Example 7> A classified fine powder and a toner 7 were obtained in the same manner as in Example 1 except that the condensate (1) was changed to the condensate (11).

Each evaluation was performed on this toner 7 in the same manner as in Example 1. The evaluation results are summarized in Tables 1 to 3.

<Example 8> A classified fine powder and toner 8 were obtained in the same manner as in Example 1 except that the condensate (1) was changed to the condensate (12).

Each evaluation was performed on this toner 8 in the same manner as in Example 1. The evaluation results are summarized in Tables 1 to 3.

<Example 9> A classified fine powder and toner 9 were obtained in the same manner as in Example 1 except that condensate (1) was changed to condensate (15).

With respect to this toner 9, each evaluation was performed in the same manner as in Example 1, except that the developing sleeve 1 was changed to the developing sleeve 2. The evaluation results are summarized in Tables 1 to 3.

<Example 10> A classified fine powder and toner 10 were obtained in the same manner as in Example 1 except that condensate (1) was changed to condensate (18).

With respect to the toner 10, the developing sleeve 1
Was changed to the developing sleeve 2, and each evaluation was performed in the same manner as in Example 1. The evaluation results are summarized in Tables 1 to 3.

Comparative Example 1 Example 1 was repeated except that the condensate (1) was changed to a condensate in which the 8-membered ring, which is the methylene bond of the unit A of the condensate (14), had 98% of the ring. In the same manner as in the above, classified fine powder and toner 11 were obtained.

Each evaluation was performed on this toner 11 in the same manner as in Example 1. The evaluation results are summarized in Tables 1 to 3.

<Comparative Example 2> Evaluations other than the offset resistance test were performed in the same manner as in Example 1 except that the developing sleeve 1 was changed to the developing sleeve 4. The evaluation results are summarized in Tables 1 to 3.

[0250]

[Table 1]

[0251]

[Table 2]

[0252]

[Table 3]

Example 11 100 parts by mass of polyester resin (52 mol% of propoxybisphenol, 30 mol% of terephthalic acid, 15 mol% of dodecenylsuccinic acid, 4 mol% of trimellitic acid, Tg = 62 ° C., Mw = 18000) 14) 2 parts by mass ・ Copper phthalocyanine 3 parts by mass

After the above materials were preliminarily mixed with a Henschel mixer, they were kneaded with a twin-screw kneading extruder set at 100 ° C. The obtained kneaded material was cooled and coarsely pulverized by a cutter mill, finely pulverized using a pulverizer using a jet stream, and classified using a multi-partition classifier utilizing the Coanda effect to obtain a volume average diameter of 8. A 6 μm classified product was obtained. Anatase-type titania fine powder (BET specific surface area 100 m ² / g) 100 produced by the sulfuric acid method was added to 100 parts by mass of the obtained classified fine powder.
1.5 parts by mass of hydrophobic silica whose parts by mass were treated with 15 parts by mass of isobutyltrimethoxysilane were added, mixed with a Henschel mixer, and sieved with a mesh having openings of 200 μm to obtain Toner 12.

The following evaluation tests were performed on the obtained toner 12.

[Image Evaluation Test] Using a commercially available color printer LBP-2030 (manufactured by Canon Inc.), the developing sleeve was replaced with the developing sleeve 3, and 3,000 sheets were printed in a normal temperature / humidity environment. And 3,000 sheets were printed under each environment of high temperature and high humidity, and the image density and fog were evaluated (evaluation environment: normal temperature / normal humidity (23 ° C./60% RH), normal temperature / low humidity (23 ° C./5) % RH), high temperature and high humidity (32.5 ° C / 80%)
RH)).

Also, after 3000 copies were made under normal temperature / normal humidity environment, a part of the developing sleeve surface was wiped cleanly with ethanol, a solid black image was printed, and the image density before and after ethanol wiping was measured. The sleeve contamination was evaluated by calculating the difference. Those having a small density difference Δ are good because they have little influence of contamination.

The image density was measured using a “Macbeth reflection densitometer” (manufactured by Macbeth). The fog is measured using a "reflection densitometer" (manufactured by Tokyo Denshoku Technology Center) to measure the reflection density of the transfer paper and the reflection density of the transfer paper after copying solid white, and the difference is used as the fog value. The smaller the value, the better the fog suppression. The measurement of fog was performed by measuring five reflection densities of a transfer material before image formation and a white background part after image formation using a reflection densitometer (reflectometer model TC-6DS manufactured by Tokyo Denshoku Co., Ltd.), and averaged. Ask for.
The difference between the reflection densities before and after image formation is evaluated as fog.

[Sleeve coat property evaluation test] The toner coat on the sleeve was visually observed, and the occurrence level of blotches was classified into the following ranks (evaluation environment: normal temperature / normal humidity (23 ° C)
/ 60% RH), room temperature / low humidity (23 ° C / 5% RH), high temperature and high humidity (32.5 ° C / 80% RH).

Blotch rank A No occurrence. B Slightly generated at the end of the sleeve. C Very slight occurrence, but does not affect the image. D: It occurs clearly and affects the image.

The sleeve ghost has a density of 1.3 and a density of 0.3.
A solid image having a density of 1.0 was copied as an original after an alternating image of a line having a width of 20 mm and a length of 100 mm (process direction) of the original No. 05 as an original, and evaluation was made based on the difference in density of the 1.0 density portion. The smaller the density difference, the better the ghost level.

[Evaluation of Density Unevenness] Images of four gradations (solid,
(Intermediate two gradations, highlight). A: All four gradations have no roughness and no density unevenness. B: Density unevenness can be confirmed in the halftone portion. C: Density unevenness and roughness are observed in the halftone portion, and the uniformity of the highlight portion is poor, but there is no practical problem. D: Density unevenness is conspicuous and practically impossible.

The evaluation results of the sleeve coat property test and the image evaluation test are summarized in Tables 4 to 6.

Example 12 100 parts by mass of polyester resin 2 parts by mass of condensate (18) 3 parts by mass of dimethylquinacridone

After premixing the above materials with a Henschel mixer, they were kneaded with a twin-screw kneading extruder set at 100 ° C. The obtained kneaded material was cooled and coarsely pulverized by a cutter mill, finely pulverized using a pulverizer using a jet stream, and classified using a multi-partition classifier utilizing Coanda effect to obtain a volume average diameter of 8. An 8 μm classified product was obtained. 100 parts by mass of the obtained classified fine particles were treated with 100 parts by mass of γ-type alumina fine powder (BET specific surface area: 120 m ² / g) produced by a pyrolysis method with 15 parts by mass of n-butyltrimethoxysilane. 1.5 parts by mass of silica was added, mixed with a Henschel mixer, and sieved with a mesh having an opening of 200 μm.
I got

Using this toner 13, the same running test as in Example 11 was performed. Tables 4 to 6 show the evaluation results of developability such as image density, fog, and density unevenness.

[0267]

[Table 4]

[0268]

[Table 5]

[0269]

[Table 6]

[0270]

According to the image forming method of the present invention, by using the specific phenol derivative condensate shown in the present invention as a charge control agent in a negatively chargeable toner, the charge characteristics and the development characteristics of the toner are significantly improved. By using a developer carrier on which a resin layer is formed on a metal substrate, the charge applying ability can be greatly improved, and the development characteristics can be improved. It is possible to stably provide a high-definition image free from a decrease in density, fog, sleeve ghost, and blotch.

[Brief description of the drawings]

FIG. 1 is a schematic view of a cross section of a part of a developer carrier of the present invention.

FIG. 2 is a cross-sectional view of a part of the developer carrier of the present invention ((A)).
(B) is a schematic diagram before polishing, and (B) is after polishing.

FIG. 3 shows an example of a developer replenishment system developing device in which the developer carrier of the present invention is incorporated (using a magnetic blade as a regulating member).
FIG.

FIG. 4 is a schematic view showing another example of a developer supply system developing device in which the developer carrier of the present invention is incorporated (using an elastic blade as a regulating member).

FIG. 5 is a schematic diagram for explaining the image forming method of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Coating layer (resin layer) 2 Conductive substance 3 Filler 4 Binder resin 5 Solid lubricant 6 Cylindrical base 7 Photosensitive drum (latent image holding body) 8 Regulator blade 9 Hopper 10 Toner 11 Magnet 12 Cylindrical base 13 Coating Layer (resin layer) 14 Developing sleeve (developer carrier) 15 Power supply 17 Elastic blade A Rotating direction of developing sleeve B Rotating direction of photosensitive drum D Developing section 501 Coating layer (resin layer) 502 Solid lubricant 503 Conductive substance 504 Filler 505 Binder resin 506 Cylindrical substrate 801 Latent image carrier 801a Photoconductive layer 801b Conductive base layer 802 Charging roller 802a Conductive elastic layer 802b Core 803 Charge bias power supply 804 Image exposure 805 Developing roller 806 Transfer roller 806a Conductivity Elastic layer 806b Core 807 Transfer bias power supply 808 Material 809 cleaning device 810 extinguishing light 811 heating and pressing means 813 a development bias power supply

Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03G 9/08 381

Claims (7)

[Claims] 1. A negatively-charged toner containing at least a binder resin and a charge control agent is transported by a developer carrier having a resin layer formed on a metal substrate, and is formed on an electrostatic latent image holder. An image forming method for developing an electrostatic latent image by transferring a negatively chargeable toner from a developer carrier to form a toner image, wherein the charge control agent is a condensate of phenol or a derivative thereof and an aldehyde. An image forming method, comprising a phenol derivative compound containing at least two or more condensates having different numbers of units, wherein the condensate is a chain condensate, a cyclic condensate, or a mixture thereof. 2. The phenol derivative compound is a condensate of phenol or a derivative thereof and an aldehyde,
2. The image forming method according to claim 1, wherein the condensate contains at least three kinds of condensates having different numbers of units, and the condensate is a chain condensate, a cyclic condensate, or a mixture thereof. . 3. The phenol derivative compound is a condensate of phenol or a derivative thereof with an aldehyde,
The condensate containing at least two kinds of condensates having 4 to 8 units, wherein the condensate is a chain condensate, a cyclic condensate, or a mixture thereof. Image forming method. 4. The phenol derivative compound is a condensate of phenol or a derivative thereof with an aldehyde,
The image forming method according to any one of claims 1 to 3, wherein the condensate is a mixture of a chain condensate and a cyclic condensate. 5. The condensate is represented by the following general formula (I) or (I)
5. The image forming method according to claim 1, further comprising a unit represented by I). Embedded image [Wherein, i represents 0 or 1, and when i is 0, R ₁ has a hydrogen atom, a halogen atom, an alkyl group, an aryl group which may have a substituent, an aralkyl group, and a substituent. Alicyclic groups, fluoroalkyl groups,
Represents a nitro group, an optionally substituted sulfone group, an optionally substituted amino group or a trialkylsilyl group, and when i is 1, R ₁ is an alkyl group or an optionally substituted aryl Group, an aralkyl group, an optionally substituted alicyclic group, an optionally substituted amino group or a trialkylsilyl group, R ₂ represents a hydrogen atom, an alkyl group, a phenyl group, an aralkyl group, -C
OR ₅ (R ₅ represents a hydrogen atom or an alkyl group) or-
(CH ₂ ) _m COOR ₆ (R ₆ represents a hydrogen atom or an alkyl group, m represents an integer of 1 to 3), and R ₃ represents a hydrogen atom, an alkyl group, a halogen atom, a carboxyl group, a hydroxy group, Cyano group, nitro group, halogenated alkyl group, trialkylsilyl group, ester group having 1 to 8 carbon atoms, amino group which may be substituted, acyl group, sulfone group which may be substituted, And R ₄ represents a hydrogen atom, an alkyl group or an aryl group. ] 6. The image forming method according to claim 1, wherein the condensate is a condensate containing a unit represented by the following general formula (III). Embedded image [R ₁ and R ₂ may be the same or different, and may have a hydrogen atom, a halogen atom, an alkyl group, an aryl group which may have a substituent, an aralkyl group, or a substituent. Represents a good alicyclic group, fluoroalkyl group, nitro group, optionally substituted sulfone group, optionally substituted amino group or trialkylsilyl group, wherein R ₃ and R ₄ are the same or different May be
Hydrogen atom, alkyl group, halogen atom, carboxyl group, hydroxy group, cyano group, nitro group, halogenated alkyl group, trialkylsilyl group, ester group having 1 to 8 carbon atoms, amino group which may be substituted, acyl group Group,
Represents an optionally substituted sulfone group or an ether group having 1 to 8 carbon atoms, and X ₁ , X ₂ , X ₃ and X _{4 each} represent a linking position and are represented by a unit represented by the general formula (II). And may form a ring by linking to the unit represented by the general formula (I) or the unit represented by the general formula (III). When the ring is a terminal, a hydrogen atom, an alkyl group or a hydroxyalkyl group is Represent. ] 7. The image forming method according to claim 1, wherein the volume average particle diameter of the toner is 6.0 μm or less.